JP3376349B2 - Triarylphosphine oxide derivatives having a fluorine-containing substituent - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a triarylphosphine oxide derivative, and more particularly, it relates to the production of a polymer having excellent chemical resistance and electrical insulation as well as adhesiveness and flame retardancy. The present invention relates to a triarylphosphine oxide derivative having a fluorine-containing substituent introduced therein, which is useful as a monomer.

[0002]

2. Description of the Related Art A polymer having excellent physical properties such as adhesiveness and flame retardancy, for example, di (3-aminophenyl) phenylphosphine oxide (DAPPO) or diaminodiphenylsulfone as a monomer for producing a polyimide resin. A method using (DDS) is known. (For example, the document MF Martinez
-Nuez et al., Polymer Prepint, 35, p.709 (1994)). However, in the case of DDS, since phosphine oxide is not contained, adhesive strength is low, and polyimide with a high genetic constant and high birefringence is produced. When DAPPO is used, adhesive strength is good, but the genetic constant and birefringence are still high. It has the disadvantage of having a high refractive index.

On the other hand, fluorine has a low surface tension due to its properties such as highest electronegativity, van derwaals radius close to hydrogen, and high binding energy with other elements. It has the peculiarity of high volatility and low friction coefficient. In particular, fluorine-containing compounds have a form in which the outside of the molecule is covered with fluorine atoms, and the chemical reactivity is lowered, improving the chemical resistance, incombustibility, heat resistance, electrical insulation, weather resistance, etc. of the compound. It occupies an important industrial position as a material for energy-related fields such as solar cells and solar cells, optical communication, application to optical materials, and materials for manufacturing next-generation semiconductors that are becoming increasingly dense. However, the fluorine compound is difficult to use because of its disadvantage that it has relatively poor adhesion to other substances, despite such excellent properties.

Therefore, in the present invention, excellent physical properties balanced by introducing a fluorine-substituted compound into a phosphine oxide compound, which is known to have an excellent effect in improving adhesive strength and flame retardancy, are imparted. It aims to provide new substances that can be made.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to simultaneously contain fluorine and phosphorus used for producing a polymer having not only chemical resistance and electrical insulation but also excellent adhesion and flame retardancy. It is to provide a novel triarylphosphine oxide derivative.

[0006]

Means for Solving the Problems and Embodiments of the Invention In order to achieve the object of the present invention, the present invention provides a triarylphosphine oxide derivative having a fluorine-substituted compound represented by the following formula 1.

[0007]

[Chemical 8] However, in the above formula, R ₁ and R ₂ are each independently a fluorine-substituted alkyl group, X is hydrogen,
It is a nitro or amine group.

The present invention also provides a method for producing the above-mentioned fluorine-substituted derivative-containing triarylphosphine oxide derivative according to the present invention, and a method for producing a polyimide using the derivative.

The present invention will be described in more detail below.

The compound of the present invention can be prepared, for example, by the following reaction formula 1
Can be manufactured by.

Reaction formula 1

[Chemical 9] However, in the above Reaction Scheme 1, R ₁ and R ₂ are as defined above.

Specifically, an organic solvent such as tetrahydrofuran and bromobenzene (compound of formula 2) disubstituted with a fluoroalkyl group in magnesium are reacted to obtain a compound of formula 3, which is then converted to diphenylphosphine. According to the invention by the Grignard reaction by reacting with Finic chloride (compound of formula 4)
(A compound represented by the formula 1a (X = H) can be obtained. At this time, the molar ratio of the reactants is in the range of 1: 1 to 1: 1.2,
Each reaction can be carried out at a temperature of 0 to 5 ° C for 3 hours and at room temperature for about 24 hours.

Then, the compound of formula (1a) above is nitrified in the presence of a salt such as sodium chloride to obtain the compound of formula (1b) (X = NO ₂ ) according to the present invention, The reaction conditions at this time were about 3 hours at a temperature of −10 to −5 ° C. and 8 hours at room temperature.
The compound of formula (1c) (X = NH ₂ ) according to the present invention can be obtained by hydrogenating the compound represented by b) in the presence of a palladium catalyst in an organic solvent such as alcohol.

The compound represented by the formula (1) of the present invention is subjected to polycondensation with a dianhydride compound by a conventional method to obtain polyamic acid, and then solution-imidized to obtain adhesiveness, It is possible to produce a polyimide polymer having excellent balance of flame retardancy, chemical resistance and electrical insulation.

The dianhydride compounds used in the production of polyimide include pyrromeric unhydride (PMDA), 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 ′ (hexadiene). Fluoropropylidene) diphthalic unhydride (6FDA), 4,4 '-(oxydiphthalic dianhydride (ODPA), etc., and all compounds known in the art can be mentioned. The polycondensation reaction between the compound and the dianhydride compound can be carried out in an organic solvent such as N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), etc. Therefore, it is possible to use a one-acting compound such as phthalic acid, etc. Also, used for solution-imidization of the polyamic acid formed by the above-mentioned polycondensation reaction. Examples of kill solvent, NM
P, o-dichlorobenzene (DCB), toluene and a mixture thereof can be mentioned, and a mixture of NMP and DCB can be preferably used. Examples of the polymer obtained from the triarylphosphine oxide derivative represented by the chemical formula 1 of the present invention include polyamides and copolymers thereof, in addition to the above-mentioned polyimide, and these are also prepared by a conventional method known in the art. Obtainable.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 3 ', 5'-bis (trifluoromethyl) phenyldiphenylphosphine oxide (compound of formula 1a; 6FP
25) with magnet rod, addition funnel, condenser and nitrogen inlet
To a 0 ml 3-neck round bottom flask was added 4.5 g of magnesium tannin (Aldrich) and 100 ml of distilled and purified tetrahydrofuran (Fisher). The temperature of the reaction mixture was lowered to 5 ° C or lower with ice water, and then 3,5-bis (trifluoromethyl)
Bromobenzene (Aldrich product) (23.5 ml) was added over 3 hours using a funnel, and then the solution was allowed to gradually reach room temperature. The reaction was further reacted at ambient temperature for 16 hours to give 3,5-bis (trifluoromethyl) phenylmagnesium bromide as a dark brown liquid.

The reaction product was further cooled to 5 ° C. or lower with ice water, and then diphenylhospicnic chloride (product of Aldrich Co.) was added thereto through an addition funnel over 3 hours. It was left to stand at room temperature. The reaction product was added and reacted at room temperature for 24 hours to obtain a brown solution close to black. After adding 10 ml of 10% sulfuric acid aqueous solution to the reaction product,
It was washed with 1 liter of water, further neutralized with sodium bicarbonate (NaHCO ₃ ), and then extracted with chloroform and water. The target compound was obtained by dissolving the solid phase residue obtained by distilling the extract under reduced pressure in 1 liter of boiling hexane, recrystallization and purification.
45 g (yield 90%) was obtained.

The compound thus obtained was dried in a vacuum oven at 60 ° C. for 6 hours and then its melting point was measured to obtain FT-IR, ¹ H-NM.
It was analyzed by R, ³¹ P-NMR and ¹⁹ F-NMR. Melting point 94.2-9
It shows the range of 5.1 ℃, and as shown in Fig. 1, it is 136 in FT-IR analysis.
Shows the CF bond peak at 3-1500cm ^-1, 1186cm- ¹
Shows a stretching peak of P = O. Also,
As shown in FIG. 2, ¹ H-NMR (solvent: DMSO-d ₆ ) analysis shows peaks at 8.46, 8.23, and 8.20 ppm, and 7.55-7.7.
From the appearance of the ¹ H peak of diphenyl at 7 ppm, it could be confirmed that the title compound was produced. Further, as shown in FIGS. 3 and 4, ³¹ P-NMR and ¹⁹ F-NMR (solvent: CDCl ₃ ) analyzes also show single peaks at 27.282 ppm and −39.663 ppm, respectively. The formation of the compound was confirmed. Example 2 Preparation of di (3-nitrophenyl) 3 ′, 5′-bis (trifluoromethyl) phenylphosphine oxide (Compound of Formula 1b; DN6FPPO) 6FPPO synthesized as in Example 1 above was treated with nitric acid and sulfuric acid. The target compound was obtained by nitrification by. Specifically, 50 g of 6FPPO and 500 ml of sulfuric acid were placed in a 1 L 3-neck round bottom flask equipped with a magnet bar, an addition funnel and a nitrogen inlet, and then melted at room temperature. The reaction mixture was adjusted to a temperature in the range of -10 to -5 ° C using NaCl and ice, and then a mixed solution of 25 ml of nitric acid and 75 ml of sulfuric acid was added through the addition funnel.
Added over time. The reaction product was allowed to stand at room temperature, and if it was at room temperature, it was further reacted for 8 hours. After the reaction was completed, the reaction product was mixed with 1 kg of ice, and if the mixture was at room temperature, it was extracted with chloroform and water. The extract was dissolved in 1 L of boiling ethanol, recrystallized and purified to obtain 55 g of the target compound (yield 92%).

The obtained compound was placed in a vacuum oven at 100 ° C. for 6 minutes.
After drying for a period of time, its melting point is measured and FT-IR, ¹
The formation of the title compound was confirmed by H-NMR, ³¹ P-NMR and ¹⁹ F-NMR analysis. Melting point is 174.5 to 175.0 ℃
As shown in FIG. 1, the asymmetric stretching peak (1534c), which is a characteristic of the aromatic nitro compound that was not shown in 6FPPO synthesized in Example 1 by FT-IR analysis, is shown.
m ^-1 ) and symmetrical stretching peak (1350 cm ^-1 ). Further, as shown in FIG. 2, ¹ H-NMR (solvent: DMSO-d ₆ )
According to the analysis, it can be known that four large peaks appeared at 7.89-8.57 ppm and NO ₂ was produced, and as shown in FIG. 3, in the ³¹ P-NMR analysis (solvent: CDCl ₃ ), N0 was generated. It is possible to know that the peak has moved from 27.282ppm to 23.432ppm due to the formation of ₂ , and it is possible to know that the purity is high by showing a single peak. However, as shown in Fig. 4, the ¹⁹ F-NMR (solvent: CDCl ₃ ) analysis showed that the fluorine peak had almost no effect of the nitration reaction, and therefore 6 FPP
It showed a single peak at 39.715 ppm, which was largely similar to O. Example 3 Preparation of di (3-aminophenyl) 3 ′, 5′-bis (trifluoromethyl) phenylphosphene oxide (Compound of Formula 1c; DN6FPPO) DN6FPPO synthesized as in Example 2 above was on activated carbon. The desired compound was obtained by reacting with hydrogen in alcohol in the presence of palladium catalyst. Specifically, 5 g of the above DN6FPPO, 250 ml of absolute ethanol and 10 wt% Pd / C
After putting 2 spun (10-15mg) into the high pressure reactor, 230rpm, 100
The reaction was carried out under hydrogen pressure of psi and temperature of 50 ° C. for 24 hours. The reaction product was filtered through activated charcoal using cellite, the solvent was evaporated, and the product was further dissolved in ethyl acetate and passed through a column packed with silica for purification. 4.5 g (yield 90%) of the target compound was obtained. After the obtained compound was purified by the sublimation method, its melting point was measured, and FT-IR, ¹ H-NMR, ³¹ P-NMR, ³¹ P-NMR, ¹⁹ F-NMR
And analyzed by elemental analyzer. Melting point 225.5 to 22
In the FT-IR analysis, as shown in Figure 1,
Primary amine stretching peaks are 3421 cm ^-1 and 3349 cm ^-1
The primary amine bending peak (bending p
Eak) was broadly represented at 1640-1560 cm ^-1 . Further, as shown in FIG. 2, according to ¹ H-NMR (solvent: DMSO-d ₆ ) analysis,
Peaks appear at 8.44, 8.14 and 8.10 ppm, 7.12
-7.28ppm, 6.86-6.92ppm, 6.34-6.81ppm and 6.60-6.7
At 4 ppm, the peaks of the 4 groups were largely observed, and 5.50 pp
At m, the amine trainer peak appeared as a single peak.

Further, the ³¹ P-NMR analysis shown in FIG. 3 (solvent: CDC
l ₃ ), the P peak is again at 28.234ppm at 23.432ppm.
The formation of amines can be seen from the migration to F., and the formation of amines has almost no effect on F. Therefore, ¹⁹ F-NMR (solvent: CDCl ₃ ) analysis shown in FIG. The peak showed a single peak at -39.594 ppm. On the other hand, in elemental analysis, the theoretical and measured values of each element are almost the same, so it is judged that the target DN6FPPO was obtained. Theoretical: C = 54.06, N = 6.30, H = 3.40, Measurement:
C = 54.02, N = 6.30, H = 3.38. Example 4 Production of Polyimide Polyimide was produced from DN6FPPO obtained in Example 3 by the following method. First, reverse Dean-Star
5g DN6FPPO while injecting nitrogen into a 3-neck round bottom flask (heated with flame before reaction to remove enough water) equipped with a k trap), drying tube, nitrogen inlet and thermometer.
And 0.008 g of phthalic acid were dried using P205, dissolved in distilled anhydrous N-methylpyrrolidone (NMP), and then the dianhydride compound (pyromellitic unhydride
(PMDA) 2.4153g, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride (BTDA) 3.5743g, 4,4'-(hexafluoropropylidene) diphthalic hydride ( 6FDA), 4.9g, 4,
In the case of 4'-oxydiphthalic dianhydride (ODPA), 3.4593 g) was added slowly. NMP was added so that the final solution would be a 15w% / v solution. The resulting solution was reacted for 24 hours at room temperature to obtain polyamic acid. Next, 7.5 g of the obtained polyamic acid was added to NMP in a volume ratio of 8: 2.
Solution-imidization was carried out in a mixture of and o-dichlorobenzene (DCB) at 180-190 ° C for 24 hours in a nitrogen atmosphere. The reaction product was allowed to reach room temperature and then precipitated with methanol to obtain a polyimide in a powder form (number average molecular weight: about 20,000). Also, for comparison, DA6F according to the invention obtained from Example 3
Instead of PPO, the conventional di (3-aminophenyl) phenylphosphine oxide (DAPPO) is reported in the literature MF Martinez-Nu.
ez et al., Polymer Prepint, 35, p.709 (1994) was used to synthesize and use the product, and diaminodiphenylsulfone DDS) was purchased from Aldrich and used. Polyimide was synthesized by a similar method. Example 5 Measurement of Physical Properties of Polyimide The polyimide resin obtained as in Example 4 was treated at room temperature for 5 hours, 100 ° C. for 5 hours, 150 ° C. for 5 hours, and 200
After being dried in a vacuum oven at 0 ° C. for 12 hours, the following chemical, thermal and optical properties were analyzed. (1) FT-IR analysis An FT-IR analyzer (Perkin-Elmer, IR-2000) was used for analysis, and the FT-IR spectrum obtained is shown in FIG. As shown in FIG. 5, the DA6FPPO-based polyimide synthesized according to the present invention has a characteristic peak of imide, C = O of polyimide is 1782, 1726 and 715 cm ⁻¹ , and CN is 13
65cm ^-1, and P = O was able to ascertain that the imidization is advanced 100% by show the absorption peak at 1188cm ^-1.

(2) Intrinsic viscosity at 25 ° C using NMP solvent Intrinsic viscosity measuring device (Canon Ubb
elohde viscometer) and the results are shown in Table 1.
It was shown to. From the results shown in Table 1, it can be seen that the polyimide according to the present invention and the comparative polyimide have similar molecular weights.

(3) Differential scan thermal analysis
ng calorimetry (DSC)) Using a differential scanning calorimeter (TA-2910) (10 ° C / min in nitrogen), free and transition temperature (Tg) values were measured, and the results are shown in Table 1. .

As can be seen from Table 1, in the case of the DA6FPPO-based polyimide produced according to the present invention, Tg is 228-281.
The temperature is shown in ° C, and the hardness of the dianhydride chain (chain
It can be seen that Tg increases as rigidity increases to ODPA, BTDA, 6FDA, and PMDA. The synthesized comparative example BTDA-DDS of 266 ° C and BTDA-DAPPO of 273 ° C were prepared for comparison with the DA6FPPO-based polyimide according to the present invention.
Showed each Tg. Conventional BTDA-DAPPO and BTDA-DDS
The reason why BTDA-DA6FPPO according to the present invention shows a lower Tg is that the free volume of DA6FPPO is increased by fluorine.
Is likely to increase.

(4) thermogravimetric anal
ysis (TGA) Tg + After bonding polyimide dried at a temperature of 50 ℃ with hot press for 5 minutes, 300psi pressure was applied for 10 minutes to obtain a flexible polyimide film with a thickness of 0.1mm (obtained The polyimide film was transparent and had a light brown color as the fluorine content increased). Thermogravimetric analysis (10 ° C./min in air) was performed on this. The results of thermogravimetric analysis are shown in Figure 6 and Figure 7 and Table 1
As shown). As can be seen from the results of thermogravimetric analysis shown in FIGS. 6 and 7 and Table 1, the DA6FPPO-based polyimide of the present invention has 400
There was no weight loss up to ℃, and the thermal stability was 6FDA, BTDA, PMDA, and OD depending on the dianhydride compound.
It increased in order of PA. Especially, the reason why 6FDA-DA6FPPO shows lower thermal stability than other DA6FPPO-based polyimides is because phosphine oxide is known to have excellent thermal stability because 6FDA has a higher molecular weight than other dianhydrides. Is judged to be contained in a relatively small amount. Further, it can be seen that the DA6FPPO-based polyimide according to the present invention remains at a weight of about 5-15 wt% even at 800 ° C. Also, it can be seen that the DA6FPPO-based polyimide according to the present invention is superior in thermal stability to the conventional BTDA-DAPPO and BTDA-DDS synthesized for comparison.

[0026]

【table 1】 (5) Solubility Measurement in Solvent The solubility test is carried out by placing 0.2 g of the polyimide film prepared as in the thermogravimetric analysis in 10 ml of an organic solvent, and then observing at room temperature for 24 hours,
Table 2 shows the test results depending on the organic solvent used.

[Table 2] From Table 2, the DA6FPPO-based polyimide according to the present invention is NMP, D
MAc (dimethylacetamide), TCE (trichloroethane),
It was dissolved in chloroform (CHCl ₃ ), and completely or partially dissolved in THF (tetrahydrofuran) or toluene (toluene). In particular, it was confirmed that 6FDA-DA6FPPO was dissolved in acetone (acetone). On the contrary, DAPPO- for comparison
The system polyimide was dissolved in NMP and DMAc, but it was completely or partially dissolved in TCE and chloroform, and in the case of DDS-system polyimide, it was only dissolved in NMP and DMAc, but not in all other solvents. .

The excellent solubility of the polyimide according to the present invention is due to the fact that Kapton® (PM
Considering the fact that DA-ODA (oxydianiline) system is not soluble in any organic solvent and its workability is not very good, it can be said that this is a great advantage.

(6) Optical Properties A thin film prepared by spin-coating a Si wafer with a polyimide solution (14 wt% in TCE) was used to measure the refractive index (Metricon Model 2010 Prism C).
(using an oupler) and the results are shown in Table 3.

[0029]

[Table 3] From Table 3 above, 6FDA-DA6FPPO containing a large amount of fluorine according to the present invention has a genetic constant (ε) of 2.355 and PMDA-OD.
Although it shows a lower value than A (2.756), it is considered that the genetic constant is not significantly affected by phosphine oxide. Birefringence (birefringenc), which is one of the most important physical properties for using polyimide as an optical device material
In e), 6FDA-DA6FPPO according to the present invention containing fluorine and phosphine oxide at the same time, PMDA-ODA (0.1
It can be seen that the value is about 100 times lower than that of 2). It can be seen that the birefringence decreases as the amount of fluorine or phosphine oxide increases, but it can be seen that phosphine oxide exhibits an effect larger than that of fluorine. It is considered that this is because triphenylphosphine oxide is not in the same plane. According to the present invention, the DA6FPPO-based polyimide containing fluorine and phosphine oxide at the same time exhibits a low genetic constant and a very low birefringence, and thus can be used very effectively as a material for semiconductor packaging and optical devices. (7) Adhesive Use the Cu foil with a thickness of 0.035 mm and the Cr / silane coated Cu foil (UCF ICF-STD.IY) provided by Iljin copper foil co. A T-peel test was performed according to ASTM D1876 and the results are shown in Table 4. The bonding conditions were such that the bonding temperature was polyimide Tg + 50 ° C., the pressure was 1000 psi, the time was 30 minutes, and the adhesive coating thickness was 0.02 ± 0.002 mm.

[Table 4] From Table 4, in the case of Cu foil coated with Cr and silane, BTDA containing most phosphine oxide
-DAPPO at 108.45 g / mm showed about 35 g / mm higher adhesion than BTDA-DDS without phosphine oxide (73 g / mm). Fluorine-containing polymers are known to exhibit extremely low adhesive strength under the influence of fluorine, but the adhesive strength of BTDA-DA6FPPO of the present invention containing phosphine oxide and fluorine at the same time is 93.31 g / mm at BTDA-. DD
The adhesive strength was 20g / mm higher than S. In the case of uncoated Cu foil, BTDA-DAPPO containing phosphine oxide (51.3 g
/ mm) shows higher adhesive strength than BTDA-DDS (34.56 g / mm), confirming that the polyimide containing phosphine oxide shows high adhesive strength, and, more specifically, it contains phosphine oxide in polyimide containing fluorine. By letting
It was confirmed that it showed high adhesive strength.

[0030]

The triarylphosphine oxide derivative having a fluorine-containing substituent according to the present invention has excellent adhesiveness,
It can be usefully utilized for the production of a polymer having excellent chemical resistance and electrical insulation as well as flame retardancy, and the obtained polymer is an intermediate substance for semiconductor packaging materials, refractory materials, optical fibers and optical materials. It can be usefully used as an intermediate substance of metal adhesives.

[Brief description of drawings]

FIG. 1 is an FT-IR analysis spectrum of the compounds synthesized in Examples 1 to 3.

FIG. 2 is a ¹ H-NMR analysis spectrum of the compounds synthesized in Examples 1 to 3.

FIG. 3 is a ³¹ P-NMR analysis spectrum of the compounds synthesized in Examples 1 to 3.

FIG. 4 is a ¹⁹ F-NMR analysis spectrum of the compounds synthesized in Examples 1 to 3.

FIG. 5: FT of polyimide prepared from the compound of the present invention
-IR analysis spectrum

FIG. 6 is a thermogravimetric analysis graph of a polyimide produced from the compound of the present invention.

FIG. 7 is a graph of thermogravimetric analysis in which a polyimide prepared from a compound of the present invention and a polyimide prepared from a conventional compound are compared and tested.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kwang Eun Jung, Republic of Korea, Gwangju Gwangyeok-si, Buk-ku, Oryon-dong, 1 Gwangju Institute of Science and Technology, New Material Science Ann Engineering (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 CAPLUS (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A fluorine-substituted triarylphosphine oxide derivative represented by the following formula (1). [Chemical 1] However, in the above formula (1), R1 and R2 are each independently a fluorine-substituted alkyl group, and X is a hydrogen group. 2. A fluorine-substituted triarylphosphine oxide derivative represented by the following formula (1). [Chemical 2] However, in the above formula (1), R1 and R2 are each independently a fluorine-substituted alkyl group, and X is a nitro group. 3. A fluorine-substituted triarylphosphine oxide derivative represented by the following formula (1). [Chemical 3] However, in the above formula (1), R1 and R2 are each independently a fluorine-substituted alkyl group, and X is an amine group. 4. A fluoroalkyl-disubstituted bromobenzene and diphenylphosphinic chloride in an organic solvent and magnesium in a ratio of 1: 1 to 1: 1.2.
The following formula (1) including reaction at a reaction molar ratio in the range of
A method for producing the compound represented by a). [Chemical 4] However, in the above formula (1a), R1 and R2 are each independently a fluorine-substituted alkyl group. 5. A fluoroalkyl-disubstituted bromobenzene and diphenylphosphinic chloride in an organic solvent and magnesium in a ratio of 1: 1 to 1: 1.2.
A method for producing a compound represented by the following formula (1b), which comprises reacting at a reaction molar ratio in the range of to obtain a compound represented by the following formula (1a) and nitrifying the compound in the presence of a salt: [Chemical 5] [Chemical 6] However, in the above formula (1b), R1 and R2 are each independently a fluorine-substituted alkyl group. 6. A fluoroalkyl-disubstituted bromobenzene and diphenylphosphinic chloride in an organic solvent and magnesium in a ratio of 1: 1 to 1: 1.2.
The compound represented by the following formula (1a) is obtained by reacting at a reaction molar ratio in the range of, and the compound is nitrated in the presence of a salt to obtain a compound represented by the following formula (1b). A method for producing a compound represented by the following formula (1c), which comprises hydrogenating in an organic solvent in the presence of a palladium catalyst: [Chemical 8] [Chemical 9] However, R1 and R2 are each independently a fluorine-substituted alkyl group. 7. A polyimide polymer obtained by reacting the fluorine-substituted triarylphosphine oxide derivative of the formula (1) according to any one of claims 1 to 3 with a dianhydride compound and then solution-imidizing the polyimide polymer. Method of manufacturing. 8. The dianhydride compound is 3,4,3'4'-
Characterized by benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-(hexafluoropropylidene) diphthalic anhydride (6FDA), 4,4' oxydiphthalic dianhydride (ODPA) or a mixture thereof The method according to claim 7, wherein